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WO1997001586A1 - Copolymere elastomere - Google Patents

Copolymere elastomere Download PDF

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Publication number
WO1997001586A1
WO1997001586A1 PCT/NL1996/000261 NL9600261W WO9701586A1 WO 1997001586 A1 WO1997001586 A1 WO 1997001586A1 NL 9600261 W NL9600261 W NL 9600261W WO 9701586 A1 WO9701586 A1 WO 9701586A1
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WO
WIPO (PCT)
Prior art keywords
group
copolymer
elastomeric copolymer
catalyst
elastomeric
Prior art date
Application number
PCT/NL1996/000261
Other languages
English (en)
Inventor
Jacob Renkema
Bernardus Johanna Muskens
Andreas Antonius Oosterlaken
Original Assignee
Dsm N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from NL1000687A external-priority patent/NL1000687C2/xx
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU62445/96A priority Critical patent/AU6244596A/en
Priority to EP96921153A priority patent/EP0835271A1/fr
Priority to BR9609483A priority patent/BR9609483A/pt
Priority to JP9504328A priority patent/JPH11509881A/ja
Priority to EA199800098A priority patent/EA199800098A1/ru
Priority to MX9800210A priority patent/MX9800210A/es
Publication of WO1997001586A1 publication Critical patent/WO1997001586A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63908—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the invention relates to an elastomeric copolymer comprising 25-85 weight % of ethylene, 15-75 weight % of ⁇ -olefine and optionally up to 20 weight % of diene, as well as to a process for the preparation of such an elastomeric copolymer.
  • An elastomeric copolymer on the basis of ethylene and an ⁇ -olefine has been known, described and prepared for a long time already.
  • Such a product has rubber-like properties and will here and in the following also be referred to as 'EAM' or 'EADM' (products based on ethylene, ⁇ -olefine and optionally diene).
  • EPM elastomeric copolymer
  • EPDM products in which the ⁇ -olefine is p_ropylene
  • Elastomeric copolymers can be characterized by means of a number of parameters. Besides the weight percentage of the monomer units there are the molecular weight (expressed as Mn [the number average molecular weight] or as Mw [the weight average molecular weight]), the molecular weight distribution or polydispersity PD (defined as Mw/Mn) , as well as the degree of branching.
  • Mn the number average molecular weight
  • Mw the weight distribution or polydispersity PD
  • degree of branching is determined on the basis of, among other things, a Mark-Houwink relation, which indicates the relation between the molecular weight (M) and the intrinsic viscosity [h of the copolymer. A less linear relation between log [h and log M indicates an increased degree of branching.
  • the experimental Mark-Houwink relation yields information on the degree of branching by comparing it with the Mark- Houwink relation for linear polymers, which is used as reference.
  • 'branching' is understood a ramification in the polymer chain that is longer than a ramification produced by the incorporation of a molecule of the ⁇ -olefine or the diene.
  • the reference Mark-Houwink relation depends on the average ethylene/ ⁇ -olefine composition of the polymer. According to Th.G. Scholte, N.L.J. Meijerink, H.M. Schoffeleers, A.M.G. Brands, J. of Appl. Pol. Sci., Vol 29, 3763-3782 (1984), for the Mark- Houwink relation of a linear ethylene-propylene (EP) copolymer it holds that:
  • C 2 and C 3 represent the content (in weight percent) of ethylene and propylene, respectively, in the copolymer
  • the referenced article also teaches how to use the Mark- Houwink relation for other types of ethylene based copolymers.
  • the degree of branching can be quantified by the branching parameter, g' (III), defined as:
  • [h b is the intrinsic viscosity of the polymer (in dl/g), and [r)] * L is the apparent intrinsic viscosity (in dl/g).
  • the apparent intrinsic viscosity [ ⁇ ] * j. of a polymer is calculated from the apparent molecular weight distribution, determined via a conventional calibration, valid for a corresponding linear EP-copolymer with a similar amount of propylene, via the relation:
  • Wi weight fraction polymer in SEC elution fraction i
  • Mi * apparent molar mass of polymer in SEC elution fraction i.
  • the elastomeric copolymer according to the invention is characterized in that the elastomeric copolymer has no crystallinity above 25°C and has a
  • the relation between the degree of branching and the molecular weight distribution in such copolymers is completely different from that of the products which have been described and known thus far.
  • the copolymers according to the invention have a much lower ⁇ value than the value corresponding to the branching characteristic according to the Mark-Houwink relation for known elastomeric copolymers.
  • the copolymers according to the invention consist of 25-85 weight % of ethylene, 15-75 weight % of an ⁇ -olefine and optionally up to 20 weight % of diene, i.e. the invention relates to EAM as well as to EADM copolymers. More preferred the ethylene content is between 40 and 70 weight %.
  • the elastomeric copolymers may also comprise more than one ⁇ -olefine and also more than one diene.
  • the polymers exibit no crystallinity above 25°C, as determined in a DSC measurement (Differential Scanning Calorimetry, in the cooling curve).
  • the new copolymers according to the invention can be characterized by substance quantities, known per se, such as molecular weight (Mw or Mn) , the polydispersity (PD) and, since they are also of an elastomeric nature, by a Mooney viscosity (M L 1+4 , 125°C).
  • Mw or Mn molecular weight
  • PD polydispersity
  • Mooney viscosity M L 1+4 , 125°C
  • the Mooney viscosity (M L 1+4 , 125°C) is measured according to ISO 289 and is a measure of the plasticity of the product.
  • the copolymer according to the invention has an Mw of at least 1000; more preferably at least 100,000. Another preference is for a copolymer having a Mooney viscosity (M L 1+4 , 125°C) of at least 20, more preferably at least 35.
  • branched copolymers of the invention are products whose ramifications are distributed virtually uniformly over all chains of the copolymer, while in conventional products they are mainly associated with the higher molecular weights.
  • the elastomeric copolymer according to the invention comprises one or more ⁇ -ole- fines.
  • such an ⁇ -olefine contains 3-25 carbon atoms (although higher ⁇ -olefines are also allowable); more preferably, the ⁇ -olefine contains 3-10 carbon atoms.
  • the ⁇ -olefine has preferably been selected from the group consisting of propylene, butene, isobutene, pentene, 4- methyl pentene, hexene, octene and ( ⁇ -methyl) styrene. Most preferably, the ⁇ -olefine is propylene, butene, hexene or octene.
  • the elastomeric copolymer comprises a diene, which for instance can have a function in a subsequent vulcanization of the elastomeric copolymer.
  • Examples of such compounds are: 1,3-butadiene, isoprene, 2,3-dimethyl butadiene 1,3, 2-ethyl butadiene 1,3, piperylene, mycrene, allene, 1,2-butadiene, 1,4,9-decatrienes, 1,4-hexadiene, 1,5-hexadiene and 4-methyl hexadiene 1,4.
  • Alicyclic polyunsaturated compounds may be either monocyclic or polycyclic.
  • examples of such compounds are norbornadiene and its alkyl derivatives; the alkylidene norbornenes, in particular the 5-alkylidene norbornenes-2, in which the alkylidene group contains 1 to 20, by preference 1 to 8 carbon atoms; the alkenyl norbornenes, in particular the 5-alkenyl norbornenes-2, in which the alkenyl group contains 2 to 20, by preference 2 to 10 carbon atoms, for instance vinyl norbornene, 5-(2 '-methyl-2 'butenyl)- norbornene-2 and 5-(3 '-methyl-2 'butenyl)-norbornene-2; dicyclopentadiene and the polyunsaturated compounds of bicyclo-(2,2,l)-heptane, bicyclo-(2,2,2)-octane, bicyclo- (3,2,l)-octane and
  • compounds such as 4,7,8,9-tetrahydroindene and isopropylidene tetrahydroindene can be used.
  • DCPD dicyclo ⁇ pentadiene
  • ENB ethylidene norbornene
  • VNB vinyl norbornene
  • HD hexadiene
  • the diene may be present in the copolymer in quantities of up to 20 weight %, more preferably however up to 10-15 weight %. Even more preferred is an amount of diene in the copolymer of 1-10 weight %, specifically between 2 and 8 weight %.
  • the elastomeric copolymer may contain an amount of extender oil.
  • This oil of a naphthenic or parafinnic nature, may be present in quantities of normally up to 250 parts by weight per 100 parts by weight of copolymer. More in particular, 15-150 parts by weight of oil per 100 parts by weight of copolymer are present.
  • the invention also relates to an elastomer composition, that is to say a compound, of which the elastomeric copolymer constitutes an essential part.
  • a compound is made up of components which are required in order to ensure the good properties of the final elastomer preparation.
  • a compound usually contains one or more of the following components: fillers, carbon black, stabilizers, antioxidants, release agents, vulcanization agents, foaming agents, vulcanization inhibitors and accelerators, oil.
  • the elastomer composition comprises a blend of the elastomeric copolymer of the invention and another thermoplastic polymer.
  • Such an other polymer can be a polyolefin (like polyethylene, polypropylene, polystyrene), a polyamide, a polyester, a polycarbonate and the like.
  • the amount of the elastomeric copolymer in such a blend can be varied, as known by the skilled man, based on the use of such a blend.
  • the blend can be a thermoplastic elastomer as well as an impact-improved thermoplast.
  • An at least partially vulcanized compound on the basis of the elastomeric copolymer also forms part of the invention.
  • the present invention therefor also relates to thermoplastic elasto ⁇ mers in which the elastomeric copolymer according to the invention forms an essential part.
  • the thermoplastic elastomer is at least partially vulcanized, as a result of which a thermoplastic vulcanizate is obtained.
  • the elastomeric copolymer of the invention can also be used as additive in lubricating oils, as a result of which another form of elastomer composition is obtained.
  • the invention also relates to a process for the preparation of the elastomeric copolymer of the invention.
  • a process for the preparation of the elastomeric copolymer of the invention comprises the polymerization of ethylene and the ⁇ -olefine, optionally in the presence of a diene, under polymerization conditions which are known per se, under the influence of a specific type of catalyst and whether or not in the presence of a cocatalyst.
  • a polymerization can take place in the gas phase as well as in a liquid reaction medium. In the latter case, solution as well as suspension polymerization can be applied.
  • the reaction is preferably carried out continuously, but semi- continuous or batchwise modes of operation are also possible.
  • RF reactivity factor
  • the RF indicates the relative affinity of the catalyst for ethylene compared with the ⁇ -olefine. The lower the RF, the lower the preference for ethylene, or the higher the affinity for the ⁇ -olefine.
  • Catalysts that are capable of producing elastomeric copolymers according to the invention have an RF ⁇ 10, preferably ⁇ 6. By nature, RF is always > 0.
  • the RF of a catalyst can be determined by carrying out a copolymerization of ethylene and an ⁇ -olefine. The RF then is the quotient of the ratios between the ethylene and ⁇ - olefine concentrations in the copolymer and the reaction medium, respectively, as expressed in the following formula:
  • a metallocene catalyst characterized by 'constraint geometry'.
  • a metallocene catalyst characterized by 'constraint geometry'.
  • Such a catalyst is described for instance in EP-A-416,815, where it is only applied, however, for the preparation of crystalline polyolefine resins having a melting point between 50 and 135°C or a melt index below 125.
  • the elastomeric copolymers according to the invention do not have a melting point or melt index in those ranges; such copolymers or their modes of preparation are not suggested, nor obtained/carried out in said EP-A-416,815.
  • the catalysts described in it, to which explicit reference is made, are only suitable if they have the reactivity factor specified in the foregoing.
  • Another type of catalyst which can meet the requirements as set forth before regarding the reactivity factors RF is a catalyst having the formula:
  • Y a cyclopentadienyl group, an amidino or phosphidino group, bonded to M
  • L a monoanionic ligand bonded to M, to the exclusion of a cyclopentadienyl group, an amidino or phosphidino group, K a neutral or anionic ligand bonded to M, m the number of K groups, n the number of R' groups bonded to D, q and s q + s > 1.
  • transition metal complexes useful in the process according to the invention are presented in Table 4.
  • the transition metal (the Me group)
  • the transition metal in the catalyst has been chosen from groups 4-6 of the Periodic Table of the Elements (see the new IUPAC notation to be found on the inside of the cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990). More preferably, the transition metal has been chosen from group 4; the highest preference is given to titanium (Ti) as transition metal.
  • the transition metal is present in reduced form in the catalyst, which means that the transition metal is in a reduced oxidation state.
  • oxidation state is meant an oxidation state which is lower than the highest possible oxidation state (at most Me 3+ for a transition metal of group 4, at most Me 4+ for a transition metal of group 5 and at most Me 5+ for a transition metal of group 6) .
  • the X group is a multidentate monoanionic ligand consisting of three components: the Y group (a cyclopentadienyl group, an amidino or phosphidino group), the connecting group (bridge) R and the DR' n or Ar group
  • a multidentate monoanionic ligand is a ligand which is bonded covalently to the transition metal at one site (the anionic site, Y) and may be bonded coordinatively to the transition metal at one (bidentate) other site or at several (tridentate, tetradentate, etc.) sites (via the D or Ar group(s)).
  • Examples of tridentate monoanionic ligands are Y-R-DR'- ⁇ -R-DR' n and Y(-R-DR' n ) 2 .
  • the Y group may be a substituted cyclopentadienyl group (Cp group), with the possibility of a substitution in the Y group being present in addition to the substitution at the Y group.
  • One or several of the substituents at the ring is the R-DR' n group or the R-Ar group.
  • Examples of an X group with such a Y group (or ligand) have the following structure (with substituents at the ring) :
  • the Cp group may also be a hetero cyclopenta ⁇ dienyl group.
  • a hetero cyclopentadienyl group in the following also referred to as 'hetero ligand' is understood to be a group that has been derived from a cyclopentadienyl group, but in which at least one of the C atoms in the 5-ring of the cyclopentadienyl has been replaced by a hetero atom, which hetero atom may be chosen from group 14, 15 or 16 of the Periodic Table of the Elements. If there is more than one hetero atom present in the 5-ring of the hetero ligand, these hetero atoms may be either the same or different.
  • the hetero atom has been chosen from group 15, while yet more preferably the hetero atom is phosphorus.
  • the hetero atom is phosphorus.
  • the M group as a rule is bonded to the Cp group via an h, 5 bond.
  • the other R' substituents at the ring of the hetero ligand may be of the same type as those which may be present at the Cp group, as represented in formula (II); the hetero ligand may also be a hetero indenyl, hetero fluorenyl or hetero benzoindenyl group.
  • the Cp group according to formula (II) is substituted with four alkyl groups (the Y group is then called a tetraalkyl- cyclopentadienyl group); more preferably, these four alkyl groups are methyl groups.
  • the Y group may (-NR'-) or a phosphidino (-PR'-) group; in other words, the Y group may also be a group which contains nitrogen (N) or phosphorus (P) and is bonded covalently to the M group as well as to the R group.
  • the R group which may also be absent (so that the DR' n or Ar group is bonded directly to the Y group (the Cp, amidino or phosphidino group)), constitutes the bond between the Y group and the DR' n or Ar group.
  • the size of the R group is critical to the extent that it determines the accessibility of the M group relative to the DR' n or Ar group, which gives the desired intramolecular coordination. If the R group (or bridge) is too short, the donor may not coordinate well due to ring tension.
  • the R groups may each separately be a hydrocarbon group with 1-20 carbon atoms (e.g. alkylidene, arylidene, aryl alkylidene, etc.). Examples of such groups are methylene, ethylene, propylene, butylene, phenylene, whether or not with a substituted side chain.
  • the R group has the following structure:
  • R' groups may each separately be as defined hereafter.
  • the main chain of the R group may also contain silicon or germanium.
  • R groups are: dialkyl silylene, dialkyl germylene, tetra- alkyl disilylene or tetraalkyl silaethylene (-SiR' 2 CR' 2 -) .
  • the alkyl groups in such a group preferably have 1-4 carbon atoms and more preferably are a methyl or ethyl group.
  • the PR'-, group This donor group consists of an electron- donating hetero atom D, chosen from group 15 or 16 of the Periodic Table of the Elements, and one or more substituents R' bonded to D.
  • the R' substituent bonded to D is as defined hereafter with the exception that it cannot be H.
  • the hetero atom D has preferably been chosen from the group comprising nitrogen (N) , oxygen (0), phosphorus (P) and sulphur (S); more preferably, the hetero atom is nitrogen (N) or phosphorus (P). It is further possible for two R' groups in the DR' n group to be connected with each other to form a ring-shaped structure (so that the DR' n group can be a pyrrolidinyl group). The DR' n group can form coordinative bonds with M.
  • the electron-donating group (or donor) used may also be a substituted or non-substituted aryl group (C 6 R' S ), such as phenyl, tolyl, xylyl, mesitylyl, cumyl, tetramethyl phenyl, pentamethyl phenyl, etc.
  • the coordination of this Ar group in relation to M may vary from 1 to h, 6 .
  • the R' groups may each separately be hydrogen or a hydrocarbon radical with 1-20 carbon atoms (e.g. alkyl, aryl, aryl alkyl and the like). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl and the like. Also, two adjacent hydrocarbon radicals may be connected with each other in a ring system; therefore the Cp group may be an indenyl, a fluorenyl or a benzoindenyl group. Such a group as well may contain one or more R' groups as substituents. R' may also be a substituent which instead of or in addition to carbon and/or hydrogen may comprise one or more hetero atoms of groups 14-16 of the Periodic Table of the Elements. Thus, a substituent may be a Si-containing group.
  • the catalyst contains two ligands L, of a monoanionic nature, which are bonded to the transition metal.
  • ligands which may be identical or different, are: a hydrogen atom, a halogen atom, an alkyl, aryl or aralkyl group, an alkoxy or aryloxy group, a group comprising a hetero atom chosen from group 15 or 16 of the Periodic Table of the Elements, for example: a sulphur compound, such as sulphite, sulphate, thiol, sulphinate, thioalkyl, a phosphorus compound, such as phosphite, phosphate.
  • Two L groups may also be connected with each other and so form a dianionic bidentate ring system.
  • L is a halogenide and/or an alkyl or aryl group; more preferably, a Cl group and/or a C ! -C 4 alkyl or a benzyl group.
  • Excluded L groups are a Cp group, an amidino group or a phosphidino group (so L cannot be a Y group).
  • the K group may be a ligand as described for the L group or a (substituted) Cp group (C 5 R' 5 ), an amido (NR' 2 ) or a phosphido group (PR' 2 ).
  • the K group may also be a neutral ligand such as an ether, an amine, a phosphine, a thioether, etc.
  • Two K groups may also be connected with each other by an R group and so form a bidentate ring system. Thus two K groups may also form together an X group. For each neutral K the value of m is higher by one than the value stated above for a monoanionic K group.
  • the X group of the transition metal consists of a Y group to which are linked one or more donor groups (the Ar groups), linked via an R group, and/or the DR' n group(s).
  • the number of donor groups is linked closely to the Y group? it is at least 1 and at most equal to the number of substitution sites that are present at a Y group.
  • a special embodiment of the catalyst useful in the invention comprises a transition metal complex in which a bidentate/monoanionic ligand is present and in which the reduced transition metal has been chosen from group 4 of the Periodic Table of the Elements and has an oxidation state of 3+.
  • the catalyst useful in the invention comprises a transition metal complex of the following structure:
  • a cocatalyst is usually applied in combination with the catalyst.
  • a cocatalyst which may be applied is one on the basis of an organometal compound.
  • the metal in such an organometal compound has been chosen from groups 1, 2, 12 or 13 of the Periodic System of the Elements.
  • For cocatalysts on the basis of aluminium compounds see for instance EP-A-287,666, pp. 20-21.
  • Suitable cocatalysts are also benzene-soluble organo-aluminium-oxy compounds as known from EP-A-360,492. Further see US-A-4,769,428
  • organo-aluminium alkyls and linear and cyclic aluminoxanes are used as cocatalyst.
  • aluminoxanes to be mentioned are methyl aluminoxanes from the producers Witco, Albemarle and Akzo.
  • linear or cyclic aluminoxanes. are used as organo-aluminium compound.
  • the quantity of cocatalyst on a molar basis relative to the quantity of complex usually amounts to 1 : 1 - 10,000 : 1, preferably 1 : 1 - 2,500 : 1 if an organometal compound is used as cocatalyst. If a compound containing or yielding a non-coordinating or loosely coordinating anion is used as cocatalyst, the ratio usually is 1 : 100 - 1,000 : 1, preferably 1 : 2 - 250 : 1.
  • the catalyst as well as the cocatalyst may be present in the catalyst composition in the form of a single component or as a mixture of several components. This may be the case in particular in those situations where it is desirable to influence the molecular properties, such as the molecular weight and in particular the molecular weight distribution.
  • the catalyst or catalyst composition according to the invention may be applied by a method known as such as a catalyst component for the polymerization to the elastomeric copolymer according to the invention.
  • the catalyst or the catalyst composition may be applied either on a carrier or without a carrier.
  • the supported catalysts are mainly used in gas phase and slurry processes.
  • the carrier used may be any carrier that is known as a catalyst carrier, for instance Si0 2 , A1 2 0 3 of MgCl 2 .
  • the carrier may be used as such, or be modified, for example by silanes, aluminiumalkyls, aluminoxanes, and others.
  • the catalyst composition may also be prepared by in-situ methods.
  • Polymerization to the elastomeric copolymer can take place in a known manner, in the gas phase as well as in a liquid reaction medium. In the latter case, both solution and suspension polymerization are suitable, with the quantity of transition metal to be used generally being such that its concentration in the dispersion agent amounts to 10 ⁇ 8 - 10 -4 mol/1, preferably 10 "7 - 10 "3 mol/1.
  • the person skilled in the art is familiar with the dispersion agent to be used in such a process.
  • the polymerization is generally carried out at temperatures between -40°C and 250°C, more preferably between -15°C and 200°C.
  • the elastomeric copolymers according to the invention can be produced at temperatures higher than the usual temperatures, with maintenance of the polymerization activity.
  • the polymerization is effected at temperatures between 35 and 180°C.
  • the pressure will usually amount to 0.1-50 MPa, although higher or lower pressures are also practicable.
  • the person skilled in the art will be very well able to obtain the desired composition of the elastomeric copolymer by adjusting the amounts of the ethylene, the ⁇ - olefine and, where applicable, the diene supplied. This also applies to adjusting and controlling of the molecular weight or the molecular weight distribution.
  • the polymerization in solution may also be performed with a higher copolymer concentration in the solution.
  • this concentration is between 10 and 45 wt .
  • the elastomeric copolymers according to the invention are suitable for a wide variety of applications, for instance for the manufacture of hoses, cables, conveyor belts, sealing profiles. They can be vulcanized by the customary methods, for instance by means of substances yielding free radicals, such as peroxides, or with sulphur. These copolymers have excellent processing characteristics. The customary techniques used to make a rubber processable can also be applied to these copolymers.
  • the invention will be elucidated by means of a few examples and comparative experiments, without being restricted thereto.
  • the elastomeric copolymers that were prepared as described in the Examples were analyzed by means of Size Exclusion Chromatography/Differential Viscosimetry Combination in accordance with the method described in the foregoing. All copolymers were elastomeric and in a DSC analysis they showed no peaks with a peak temperature higher than 25°C; most copolymers showed no peaks at temperatures higher than 0°C.
  • the equipment and the experimental conditions for this SEC-DV analysis were as follows:
  • Viscotek and high-sensitivity accessory (Waters); Data processing; Viscotek data processing software,
  • SEAC sesquiethylaluminumchloride
  • B(C 6 F 5 ) 4 dimethylanilinium pentafluorophenyl borate
  • Continuous polymerization A number of continuous flows of petrol, propylene, ethylene and optionally diene, catalyst and cocatalyst were supplied to a 1.5-litre reactor. All starting materials were freed of oxygen by means of a Cu- deoxo catalyst, and of polar components by means of columns with molecular sieves type 4A. The solution thus obtained was removed continuously from the reactor. In a flash vessel the catalyst components were deactivated with isopropyl alcohol, the monomers were flashed and the solution was stabilized with about 1000 ppm of Irganox 1076®. After working up, the polymer was analyzed.
  • the quantities of ethylene and propylene are expressed in normal litres per hour (nl/h), "normal litre” being a litre at a pressure of 0.1 MPa and a temperature of 25°C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Copolymère élastomère comportant de 25 à 85 % en poids d'éthylène, de 15 à 75 % en poids d'une α-oléfine, et éventuellement jusqu'à 20 % en poids de diène. Ce copolymère est caractérisé en ce qu'il présente un coefficient de ramification constant (UBC) qui satisfait la relation (a). L'invention concerne également un procédé de préparation d'un tel copolymère élastomère, consistant à utiliser un catalyseur dont le facteur de réactivité est inférieur à 10.
PCT/NL1996/000261 1995-06-29 1996-06-26 Copolymere elastomere WO1997001586A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU62445/96A AU6244596A (en) 1995-06-29 1996-06-26 Elastomeric copolymer
EP96921153A EP0835271A1 (fr) 1995-06-29 1996-06-26 Copolymere elastomere
BR9609483A BR9609483A (pt) 1995-06-29 1996-06-26 Copolímero elastomérico
JP9504328A JPH11509881A (ja) 1995-06-29 1996-06-26 エラストマー状コポリマー
EA199800098A EA199800098A1 (ru) 1995-06-29 1996-06-26 Эластомерный сополимер, эластомерная композиция, способ получения эластомерного сополимера, изделие
MX9800210A MX9800210A (es) 1995-06-29 1996-06-26 Copolimero elastomerico.

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US64795P 1995-06-29 1995-06-29
NL1000687A NL1000687C2 (en) 1995-06-29 1995-06-29 Ethylene-~a-olefin(-diene) copolymer for prodn. of thermoplastic elastomers
US60/000,647 1995-06-29
NL1000687 1995-06-29
EP96201116 1996-05-03
EP96201116.9 1996-05-03
US1884996P 1996-05-30 1996-05-30
US60/018,849 1996-05-31

Publications (1)

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WO1997001586A1 true WO1997001586A1 (fr) 1997-01-16

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Country Status (9)

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EP (1) EP0835271A1 (fr)
JP (1) JPH11509881A (fr)
KR (1) KR19990028655A (fr)
AU (1) AU6244596A (fr)
BR (1) BR9609483A (fr)
CA (1) CA2225742A1 (fr)
EA (1) EA199800098A1 (fr)
MX (1) MX9800210A (fr)
WO (1) WO1997001586A1 (fr)

Cited By (9)

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WO1998049229A1 (fr) * 1997-04-29 1998-11-05 The Dow Chemical Company Copolymeres amorphes de propylene-polyene et compositions connexes
WO1998049212A1 (fr) * 1997-04-30 1998-11-05 The Dow Chemical Company Interpolymeres d'etylene/alpha-olefine/diene et leur preparation
NL1006421C2 (nl) * 1997-06-27 1998-12-29 Dsm Nv Elastomeer copolymeer.
WO1999000434A1 (fr) * 1997-06-27 1999-01-07 Dsm N.V. Copolymere elastomere et procede de preparation
WO2000037514A1 (fr) * 1998-12-21 2000-06-29 Exxon Chemical Patents Inc. Compositions ramifiees semi-cristallines a base d'ethylene-propylene
EP1921096A1 (fr) * 2005-08-10 2008-05-14 Mitsui Chemicals, Inc. Caoutchouc copolymère, compositions de caoutchouc et moulages de caoutchouc
EP2058339A1 (fr) * 2007-11-09 2009-05-13 Borealis Technology OY Copolymère de polyéthylène
US8124707B2 (en) 2003-07-09 2012-02-28 Dsm Ip Assets B.V. Process for the production of a polymer comprising monomeric units of ethylene, an A-olefin and a vinyl norbornene
WO2014077429A1 (fr) * 2012-11-14 2014-05-22 주식회사 엘지화학 Copolymère élastique ternaire et procédé pour le préparer

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KR101585206B1 (ko) * 2013-07-22 2016-01-13 주식회사 엘지화학 디엔을 포함하는 3원계 탄성 공중합체 및 이의 제조 방법
KR102659554B1 (ko) * 2018-11-26 2024-04-24 롯데케미칼 주식회사 인장신율과 복원력이 우수한 복합수지 조성물

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EP0552946A1 (fr) * 1992-01-23 1993-07-28 Mitsui Petrochemical Industries, Ltd. Elastomère de copolymère éthylène/alpha-oléfine/7-méthyl-1,6-octadiène et compositions le contenant
WO1993025591A1 (fr) * 1992-06-18 1993-12-23 Spherilene S.R.L. Procede de preparation d'un copolymere ethylenique
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WO1996012744A1 (fr) * 1994-10-24 1996-05-02 Exxon Chemical Patents Inc. Polymeres ramifies a longue chaine et leur production
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EP0347129A1 (fr) * 1988-06-16 1989-12-20 Exxon Chemical Patents Inc. Procédé de production d'élastomères EPDM à haut poids moléculaire en utilisant un système catalytique métallocène-alumoxane
WO1993008221A2 (fr) * 1991-10-15 1993-04-29 The Dow Chemical Company Polymeres olefiniques elastiques sensiblement lineaires
EP0552946A1 (fr) * 1992-01-23 1993-07-28 Mitsui Petrochemical Industries, Ltd. Elastomère de copolymère éthylène/alpha-oléfine/7-méthyl-1,6-octadiène et compositions le contenant
WO1993025591A1 (fr) * 1992-06-18 1993-12-23 Spherilene S.R.L. Procede de preparation d'un copolymere ethylenique
WO1994013715A1 (fr) * 1992-12-17 1994-06-23 Exxon Chemical Patents Inc. Procede a dilution destine a la preparation d'un copolymere d'ethylene/alpha-olefine et consistant a utiliser des systemes catalyseurs a alliage organometallique
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WO1996012744A1 (fr) * 1994-10-24 1996-05-02 Exxon Chemical Patents Inc. Polymeres ramifies a longue chaine et leur production
WO1996015161A1 (fr) * 1994-11-14 1996-05-23 Dsm N.V. Systeme catalyseur pour la preparation d'un copolymere semblable a du caoutchouc

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998049229A1 (fr) * 1997-04-29 1998-11-05 The Dow Chemical Company Copolymeres amorphes de propylene-polyene et compositions connexes
WO1998049212A1 (fr) * 1997-04-30 1998-11-05 The Dow Chemical Company Interpolymeres d'etylene/alpha-olefine/diene et leur preparation
US6465584B1 (en) 1997-06-27 2002-10-15 Dsm N.V. Elastomeric copolymer and process for the preparation thereof
NL1006421C2 (nl) * 1997-06-27 1998-12-29 Dsm Nv Elastomeer copolymeer.
WO1999000434A1 (fr) * 1997-06-27 1999-01-07 Dsm N.V. Copolymere elastomere et procede de preparation
JP2002507228A (ja) * 1997-06-27 2002-03-05 ディーエスエム エヌ．ブイ． 弾性共重合体及びその製造方法
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WO2000037514A1 (fr) * 1998-12-21 2000-06-29 Exxon Chemical Patents Inc. Compositions ramifiees semi-cristallines a base d'ethylene-propylene
US6573350B1 (en) 1998-12-21 2003-06-03 Exxonmobil Chemical Patents, Inc. Branched semi-crystalline high-C3 ethylene-propylene compositions
US8124707B2 (en) 2003-07-09 2012-02-28 Dsm Ip Assets B.V. Process for the production of a polymer comprising monomeric units of ethylene, an A-olefin and a vinyl norbornene
EP1921096A1 (fr) * 2005-08-10 2008-05-14 Mitsui Chemicals, Inc. Caoutchouc copolymère, compositions de caoutchouc et moulages de caoutchouc
EP1921096A4 (fr) * 2005-08-10 2009-08-12 Mitsui Chemicals Inc Caoutchouc copolymère, compositions de caoutchouc et moulages de caoutchouc
EP2058339A1 (fr) * 2007-11-09 2009-05-13 Borealis Technology OY Copolymère de polyéthylène
WO2009059781A1 (fr) * 2007-11-09 2009-05-14 Borealis Technology Oy Copolymère de polyéthylène
WO2014077429A1 (fr) * 2012-11-14 2014-05-22 주식회사 엘지화학 Copolymère élastique ternaire et procédé pour le préparer
US9382360B2 (en) 2012-11-14 2016-07-05 Lg Chem, Ltd. Elastic terpolymer and preparation method thereof

Also Published As

Publication number Publication date
CA2225742A1 (fr) 1997-01-16
MX9800210A (es) 1998-04-30
KR19990028655A (ko) 1999-04-15
EP0835271A1 (fr) 1998-04-15
BR9609483A (pt) 1999-03-02
EA199800098A1 (ru) 1998-08-27
JPH11509881A (ja) 1999-08-31
AU6244596A (en) 1997-01-30

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